Methine dyes from 1-[2-[(2-benzothiazolyl)thio]alkyl]-1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinoline compounds

ABSTRACT

Methine dyes from tetrahydroquinoline compounds containing N-thioether substituents, in general produce bright yellow shades when applied to polyester fabrics by conventional dyeing procedures, have improved properties such as dyeability, fastness to light, resistance to sublimation, insensitivity to pH changes, and dye at the boil and under pressure to the same depth of shade. These compounds are particularly useful in the thermal fixation technique for dyeing polyester materials.

The methine dyes of this invention derived from N-substitutedtetrahydroquinoline compounds generally produce bright yellow shades onpolyester fabrics and have one or more improved properties such asdyeability, fastness to light and crock, wash resistance to sublimation,good Barre' coverage and leveling. The dyes generally are insensitive topH changes, dye at the boil and under pressure to the same depth ofshade, and are particularly useful in the thermal fixation technique fordyeing polyester materials.

The dyes of this invention have the following generic formula: ##STR1##wherein X is selected from cyano, carbamoyl, lower alkyl carbamoyl,lower alkoxycarbonyl, lower alkylsulfonyl and arylsulfonyl; R, R¹, andR² are independently selected from hydrogen and lower alkyl; R³ isselected from hydrogen, lower alkyl, lower alkoxy, fluorine, chlorineand bromine, and n is 0, 1 or 2; R⁴ is lower alkylene; R⁵ is selectedfrom hydroxyethyl, acyloxyethyl and substituted and unsubstitutedphenyl, benzyl, phenylethyl, cyclohexyl, pyridyl, quinolyl andpyrimidinyl radicals, and azolyl radicals having the formula ##STR2##wherein Y is an ethylenically-unsaturated, two-atom chain of carbonatoms or a nitrogen and a carbon atom, X is an oxygen or sulfur atom orwhen Y is a two-atom carbon chain of atoms X can be a nitrogen atom, andwhen Y is a chain of two nuclear carbons of a phenylene ring, saidazolyl radicals can be benzothiazolyl, benzoxazolyl or benzimidazolyl,each of which may be substituted with up to two groups independentlyselected from F, Cl, Br, NO₂, lower alkyl, lower alkylamino, loweralkanoylamino, lower alkoxy, hydroxy and cyano. The term "lower" as usedherein is from 1-8 carbons.

The R⁵ phenyl, benzyl and cyclohexyl radicals may be substituted withsuch groups as lower alkyl, lower alkoxy, lower alkoxycarbonyl, loweralkylether, hydroxy, cyano, flourine, chlorine, bromine and nitro.Typical are p-chlorophenyl, m-bromophenyl, m-nitrophenyl, p-tolyl,p-anisyl, o,p-dichlorophenyl, p-butoxyphenyl, p-ethylphenyl,p-ethylbenzyl, p-methoxybenzyl, m-bromobenzyl, o,p-dichlorobenzyl,p-methoxycarbonylbenzyl, p-hydroxybenzyl, m-cyanobenzyl,3-methylcyclohexyl, 4-methylcyclohexyl and 3,3,5-trimethylcyclohexyl.The pyridyl, quinolyl and pyrimidinyl radicals may be substituted withlower alkyl, such as 4-methyl-2-pyridyl, 7-ethyl-2-quinolyl and4,6-dimethyl-2-pyrimidinyl.

The --X--Y-- atoms of above R⁵ may complete, for example, ##STR3## Thecarbons and any secondary nitrogen atoms of these radicals may besubstituted, such as, 5-phenyl-1,3,4-oxazol-2-yl,5-acetamido-1,3,4-thiadiazol-2-yl, 6-methyl-2-benzothiazolyl,4,6-dichloro-2-benzothiazolyl, 6-cyano-2-benzoxazolyl,6-methylsulfonyl-2-benzothiazolyl, 5-methoxy-2-benzoxazolyl,6-nitro-2-benzothiazolyl, 2-benzimidazolyl,6-thiocyano-2-benzothiazolyl, 2-thiazolyl, and4,6-di-bromo-2-benzothiazolyl.

Preferred groups represented by R⁵ have the formulae ##STR4## whereinR¹¹ is hydrogen, lower alkyl, lower alkoxy, F, Cl or Br;

R¹² is hydrogen, lower alkanoylamino or lower alkylsulfonamido;

R¹³ is hydrogen, lower alkyl, phenyl or phenyl substituted with loweralkyl, lower alkoxy, F, Cl or Br;

R¹⁴ is hydrogen, lower alkyl, lower alkoxy, F, Cl, Br, nitro, loweralkylsulfonyl, cyano or thiocyanato;

R¹⁵ is hydrogen or lower alkyl;

X is --O--, --S-- or --NH--; and

n' is 1 or 2; and

n is 0, 1 or 2.

The most preferred group of the above dyes are of the generic formula ofpage 2 wherein R, R¹, R² and R³ are individually selected from hydrogenand methyl, X is cyano, R⁴ is ethylene, and R⁵ is 2-benzothiazolyl or2-benzoxazolyl. Of these, the preferred dye is R, R¹ and R² as methyl,R³ as hydrogen, X as cyano, and R⁵ as 2-benzothiazolyl. This dye hasparticularly exceptional sublimation fastness, fastness to light, crockfastness, pH stability, build-up, leveling properties and good energy ofapplication properties.

These compounds are particularly distinguished from the previously knowntetrahydroquinoline methine dyes, such as those disclosed in U.S. Pat.No. 3,247,211 and U.S. Pat. No. 3,240,783 by improved pH stability. Thepreviously known tetrahydroquinoline compounds have been limited inutility in the dyeing of polyester fabrics because of loss of colorunder high pH (6-8) conditions during the dyeing operation. The subjectdyes are stable at high pH and result in full color yield and completeutilization of the dye even at pH levels of 8 or above.

The quinoline compounds used as starting materials for the present dyesare described in Elderfield's review (R. C. Elderfield, "HeterocyclicCompounds," Volume 4, John Wiley and Sons, Inc., New York, New York,1952). Other references are J. Gagan and D. Lloyd, Chem. Communications,1967, pp 1043-1044, Roberts and Turner, J. Chem. Soc., 1927, 1832,Houben-Weyl, Volume II, Part 3, p. 326, R. M. Acheson, "An Introductionto the Chemistry of Heterocyclic Compounds," Interscience Publishers,Inc., New York, New York, 1960, Chapter VI. The reduction of thequinoline compounds to the 1,2,3,4-tetrahydroquinoline derivatives is awell-known reaction.

PREPARATION OF N-HALOALKYLTETRAHYDROQUINOLINE INTERMEDIATES Example 1

350.0 Grams 2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline, 2000 mlethanol, and 110 grams ethylene oxide are heated in an autoclave for 12hours at 180° C. The alcohol is removed by distillation and thehydroxylated product crystallizes and is collected by filtration, givinga product melting at 66°-68° C.

Example 2

219 Grams 1-(2-hydroxyethyl)-2,2,4-trimethyl-1,2,3,4-tetrahydroquinolineare added to 250 grams phosphorus oxychloride at such a rate that thetemperature is maintained at 30°-40° C. The reaction is heated for twohours at 95° C., the reaction drowned in ice water (5-6 liters), thechlorinated product crystallized and collected by filtration. Theproduct melts at 48°-49° C.

Examples of other N-haloalkyltetrahydroquinolines that can be preparedas above or by reaction with epichlorohydrin followed by simpleacylation, include

Example 3

N-(2-chloroethyl)-1,2,3,4-tetrahydroquinoline.

Example 4

N-(2-chloroethyl)-2,7-dimethyl-1,2,3,4-tetrahydroquinoline.

Example 5

N-(2-chloropropyl)-2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline.

Example 6

N-(3-chloro-2-hydroxypropyl)-2,2,4-trimethyl-7-bromo-1,2,3,4-tetrahydroquinoline.

Example 7

N-(2-chloroethyl)-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline.

Example 8

N-(2-acetoxy-3-chloropropyl)-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline.

PREPARATION OF THE ALDEHYDE INTERMEDIATES Example 9

25.2 Grams1-(2-chloroethyl)-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline, 13.8grams potassium carbonate, 16.7 grams 2-mercaptobenzothiazole, and 100ml dimethylformamide are refluxed for two hours, the reaction drowned inwater, and the product extracted with chloroform to give 38 grams of thefollowing structure: ##STR5##

Example 10

38.2 Grams1-[2-[(2-benzothiazolyl)thio]ethyl]-1,2,3,4-tetrahydro-2,2,4,7-tetramethylquinolineare dissolved in 100 ml of dimethylformamide. To this is added 15.3grams phosphorus oxychloride at 15°-20° C. After heating for one hour at95° C., the reaction mixture is drowned in ice water, made basic with50% sodium hydroxide and allowed to stand a few hours until the productsolidifies. The aldehyde intermediate is collected by filtration, washedwith water, and air dried. The product has the structure: ##STR6##

Example 11

25.2 Grams1-(2-chloroethyl)-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline, 13.8grams potassium carbonate, 11.1 grams benzenethiol and 150 mldimethylformamide are refluxed for two hours, the reaction drowned inwater, the product collected by filtration, washed with water, and driedin air. After recrystallization from methanol, the product has thefollowing structure: ##STR7##

Example 2

1.4 grams1-(2-chloroethyl)-6-formyl-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinoline,0.8 gram 2-mercaptobenzoxazole, 0.8 gram potassium carbonate, and 20 mldimethylformamide are heated at 140° C. with stirring for one hour. Thereaction mixture is drowned in water, and the product collected byfiltration to yield 1.95 grams of the following structure: ##STR8##

EXAMPLES OF DYE PREPARATION Example 13

4.1 Grams aldehyde from Example 10, 0.7 grams malononitrile, 0.2 mlpiperidine, and 50 ml of methyl cellosolve are heated at 95° C. for onehour. The dye which separated upon cooling is collected by filtration,washed with methanol, and air-dired. The product which melts at 209°-11°C. dyes polyester fibers deep shades of yellow and has the formula:##STR9##

Example 14

To a mixture of 125.0 grams1-(2-hydroxyethyl)-2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline in 125 mlof dimethylformamide is added, below 90° C., 125 ml of phosphorusoxychloride. The reaction mixture is heated two hours at 100° C.,cooled, and neutralized to pH 5-6 with potassium carbonate. A quantity,95.0 grams, 2-mercaptobenzothiazole is added and the mixture refluxedfor one hour. After cooling to 45°-50° C., a slurry of 186 grams sodiumacetate and 46.5 grams malononitrile in 800 ml isopropanol is added. Theresulting mixture is refluxed for 2.0 hours. The reaction is cooled andwater slowly added. The dye is collected by filtration, washed withwater, and air dried. The product which melts at 165°-167° C. dyespolyester fibers bright yellow shades and has the following structure:##STR10##

Example 15

3.8 Grams of the aldehyde of Example 12, 1.0 gram methyl cyanoacetate,25 ml alcohol, and 0.2 ml piperidine are refluxed together for one hour.The reaction mixture is allowed to cool and the product collected byfiltration, washed with ethanol, and air dried. The product dyespolyester fibers deep shades of yellow and has the formula: ##STR11##

Example 16

13.7 Grams1-[2-[(2-benzothiazolyl)thio]ethyl]-6-formyl-1,2,3,4-tetrahydro-2,2,4-trimethylquinoline,18.0 grams phenylsulfonylacetonitrile, 0.4 ml piperidene, and 100 mlethanol are refluxed together for one hour. The reaction mixture isallowed to cool and the yellow product collected by filtration and airdried. The product colors polyester fiber yellow and has the formula:##STR12##

The dyes in the following table are prepared by the proceduresillustrated above and have the following general formula: ##STR13##

    __________________________________________________________________________    Example         Substituents                                                  No.  X          R, R.sup.1, R.sup.2, R.sup.3                                                                 R.sup.4       R.sup.5                          __________________________________________________________________________    17   CN         NONE           CH.sub.2 CH.sub.2                              18   CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR14##                       19   CN         2,7-di-CH.sub.3                                                                              CH.sub.2 CH.sub.2                                                                            ##STR15##                       20   CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR16##                       21   SO.sub.2 C.sub.6 H.sub.5                                                                 2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR17##                       22   COOCH.sub.3                                                                              2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR18##                       23   CONH.sub.2 2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR19##                       24   CONHC.sub.2 H.sub.5                                                                      2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR20##                       25   SO.sub.2 CH.sub.3                                                                        2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2 CH.sub.2                                                                   ##STR21##                       26   CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR22##                       27   CN         2,7-di-CH.sub.3                                                                              CH.sub.2 CH.sub.2                                                                            ##STR23##                       28   CN         NONE           CH.sub.2 CH.sub.2                                                                            ##STR24##                       29   CN         7-Br-2,2,4-tri-CH.sub.3                                                                      CH.sub.2 CH.sub.2                                                                            ##STR25##                       30   CN         2-CH.sub.37-OCH.sub.3                                                                        CH.sub.2 CH.sub.2                                                                            ##STR26##                       31   CN         7-CH.sub.3     CH.sub.2 CH.sub.2                                                                            ##STR27##                       32   SO.sub.2 C.sub.6 H.sub.4 -p-Cl                                                           2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR28##                       33   COOC.sub.2 H.sub.5                                                                       2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR29##                       34   CN         2,2,4-tri-CH.sub.3                                                                            ##STR30##                                                                                   ##STR31##                       35   CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR32##                       36   CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                           C.sub.6 H.sub.11                 37   CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                           CH.sub.2 C.sub.6 H.sub.5         38   CONH.sub.2 2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH(OH)CH.sub.2                                                                     CH.sub.2 C.sub.6 H.sub.5         39   CN         2,2,4-tri-CH.sub.3                                                                           (CH.sub.2).sub.4                                                                            CH.sub.2 C.sub.6 H.sub.5         40   CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH(OCCCH.sub.3)CH.sub.2                                                            CH.sub.2 C.sub.6 H.sub.5         41   CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH(OCCCH.sub.3)CH.sub.2                                                             ##STR33##                       42   CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR34##                       43   COOC.sub.2 H.sub.5                                                                       2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR35##                       44   SO.sub.2 CH.sub.3                                                                        2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR36##                       45   CONHC.sub.2 H.sub.5                                                                      2,2,4-tri-CH   CH.sub.2 CH.sub.2                                                                            ##STR37##                       46   CONHC.sub.2 H.sub.5                                                                      2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR38##                       47   CONHC.sub.2 H.sub.5                                                                      NONE           CH.sub.2 CH.sub.2                                                                            ##STR39##                       48   CN         NONE           CH.sub.2 CH.sub.2                                                                            ##STR40##                       49   CN         2,7-di-CH.sub.3                                                                              CH.sub.2 CH.sub.2                                                                            ##STR41##                       50   SO.sub.2 C.sub.6 H.sub.5                                                                 2,7-di-CH.sub.3                                                                              CH.sub.2 CH.sub.2                                                                            ##STR42##                       51   SO.sub.2 C.sub.6 H.sub.5                                                                 7-CH.sub.3     CH.sub.2 CH.sub.2                                                                            ##STR43##                       52   CN         2-CH(CH.sub.3).sub.2                                                                         CH.sub.2 CH.sub.2                                                                            ##STR44##                       53   CN         2,5,7-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR45##                       54   CN         7-OCH.sub.3 -2,2,4-tri-CH.sub.3                                                              CH.sub.2 CH.sub.2                                                                            ##STR46##                       55   COOCH.sub.3                                                                              2,2,4,7-tetra-CH.sub.3                                                                        CH.sub.2 CH.sub.2                                                                           ##STR47##                       56   CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR48##                       57   CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR49##                       58   CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR50##                       59   CONH.sub.2 2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR51##                       60   SO.sub.2 CH.sub.3                                                                        2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR52##                       61   CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR53##                       62   CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR54##                       63   COOC.sub.2 H.sub.5                                                                       2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR55##                       64   COOC.sub.2 H.sub.5                                                                       2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR56##                       65   SO.sub.2 C.sub.6 H.sub.4 -p-CH.sub.3                                                     2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR57##                       66   CONHC.sub.2 H.sub.5                                                                      2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR58##                       67   CONHC.sub.2 H.sub.5                                                                      2,7-di-CH.sub.3                                                                              CH.sub.2 CH.sub.2                                                                            ##STR59##                       68   CN         2,7-di-CH.sub.3                                                                              CH.sub.2 CH.sub.2                                                                            ##STR60##                       69   CN         NONE           CH.sub.2 CH.sub.2                                                                            ##STR61##                       70   CN         7-Br-2,2,4-tri-CH.sub.3                                                                      CH.sub.2 CH.sub.2                                                                            ##STR62##                       71   CN         2-CH.sub.37-CH.sub.3                                                                         CH.sub.2 CH.sub.2                                                                            ##STR63##                       72   CN         2,2,4-tri-CH.sub.3 -5,8-di-OCH.sub.3                                                         CH.sub.2 CH.sub.2                                                                            ##STR64##                       73   CN         2,2,4,7-tetra-CH.sub.3                                                                       (CH.sub.2).sub.4                                                                             ##STR65##                       74   CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH(OH)CH.sub.2                                                                      ##STR66##                       75   CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH(OCOCH.sub.3)CH.sub.2                                                             ##STR67##                       76   CN         2-CH.sub.3     CH.sub.2 CH.sub.2                                                                            ##STR68##                       77   CN         2-CH(CH.sub.3).sub.2                                                                         CH.sub.2 CH.sub.2                                                                            ##STR69##                       78   CO.sub.2 CH.sub.3                                                                        2-CH)CH.sub.3).sub.2                                                                         CH.sub.2 CH.sub.2                                                                            ##STR70##                       79   CO.sub.2 CH.sub.3                                                                        2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR71##                       80   CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR72##                       81   CONHC.sub.4 H.sub.9 -n                                                                   2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR73##                       82   CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR74##                       83   CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR75##                       84   CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR76##                       85   SO.sub.2 C.sub.6 H.sub.5                                                                 2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR77##                       86   COOC.sub.2 H.sub.5                                                                       2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR78##                       87   COOC.sub.2 H.sub.5                                                                       2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                           C.sub.6 H.sub.5                  88   COOC.sub.2 H.sub.5                                                                       2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.2                                                                  C.sub.6 H.sub.5                  89   CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.2                                                                  C 6 H.sub.5                      90   CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                           C.sub.6 H.sub.5                  91   CN         2.2.4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR79##                       92   SO.sub.2 CH.sub.3                                                                        2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR80##                       93   CONH.sub.2 2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR81##                       94   CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR82##                       95   CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR83##                       96   CN         2,2,4,7-tetra-CH.sub.3                                                                       (CH.sub.2).sub.4                                                                             ##STR84##                       97   CONH.sub.2 2,2,4,7-tetra-CH.sub.3                                                                       (CH.sub.2).sub.4                                                                             ##STR85##                       98   SO.sub.2 C.sub.6 H.sub.5                                                                 2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR86##                       99   COOC.sub.2 H.sub.5                                                                       2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR87##                       100  COOC.sub.3 H.sub.7 -n                                                                    2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR88##                       101  COOC.sub.2 H.sub.5                                                                       2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR89##                       102  CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR90##                       103  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR91##                       104  COOCH.sub.3                                                                              2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR92##                       105  COOCH.sub.3                                                                              2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR93##                       106  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR94##                       107  CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR95##                       108  CN         7-Br-2,2,4-tri-CH.sub.3                                                                      CH.sub.2 CH.sub.2                                                                            ##STR96##                       109  CN         2-CH.sub.3     ab,4 CH.sub.2 CH.sub.2                                                                       ##STR97##                       110  CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR98##                       111  COOCH.sub.3                                                                              2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR99##                       112  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR100##                      113  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR101##                      114  SO.sub.2 C.sub.6 H.sub.5                                                                 2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR102##                      115  SO.sub.2 C.sub.6 H.sub.5                                                                 2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                           C.sub.6 H.sub.4 p-Cl             116  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                           C.sub.6 H.sub.4 p-Cl             117  CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                           C.sub.6 H.sub.4 p-Cl             118  CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR103##                      119  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR104##                      120  CN         2,2,4,7-tetra-CH.sub.3                                                                       (CH.sub.2).sub.3                                                                             ##STR105##                      121  CONHC.sub.4 H.sub.5                                                                      2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2).sub.3                                                                              ##STR106##                      122  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR107##                      123  CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR108##                      124  COOC.sub.2 H.sub.5                                                                       2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR109##                      125  CONH.sub.2 2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR110##                      126  CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                           C.sub.6 H.sub.11                 127  COOCH.sub.3                                                                              2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                           C.sub.6 H.sub.10 -3-CH.sub.3                                                  7                                128  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                           C.sub.6 H.sub.                                                                10 -3-CH.sub.3                   129  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR111##                      130  COOCH.sub.3                                                                              2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR112##                      131  COOCH.sub.3                                                                              2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR113##                      132  CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR114##                      133  COOC.sub.2 H.sub.5                                                                       2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR115##                      134  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR116##                      135  CONH.sub.2 2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR117##                      136  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR118##                      137  SO.sub.2 C.sub.6 H.sub.5                                                                 2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR119##                      138  SO.sub.2 C.sub.6 H.sub.5                                                                 2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR120##                      139  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR121##                      140  CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR122##                      141  COOCH.sub.3                                                                              2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR123##                      142  COOCH.sub.3                                                                              2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                           CH.sub.2 C.sub.6                                                              H.sub.4p-Cl                      143  SO.sub.2 CH.sub.3                                                                        2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                           CH.sub.2 C.sub.6 H.sub.4p-Cl                                                  2                                144  SO.sub.2 CH.sub.3                                                                        2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                           C.sub.6 H.sub.4p-C(CH.sub.3).                                                 sub.2                            145  CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR124##                      146  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                           C.sub.2 H.sub.4 OH               147  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.2                                                                  C.sub.2 H.sub.4 C.sub.6                                                       H.sub.5                          148  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2 CH.sub.2                                                                   ##STR125##                      149  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                            ##STR126##                      150  CN         2,2,4-tri-CH.sub.3                                                                           CH.sub.2 CH.sub.2                                                                            ##STR127##                      151  CN         2,2,4,7-tetra-CH.sub.3                                                                       CH.sub.2 CH.sub.2                                                                           C.sub.6 H.sub.4p-CH.sub.3        __________________________________________________________________________

the invention has been described in detail with particular reference tocertain preferred embodiments thereof, but it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention.

We claim:
 1. Compounds of the formula: ##STR128## wherein X is selectedfrom cyano, carbamoyl, lower alkyl carbamoyl, lower alkoxycarbonyl,lower alkylsulfonyl and arylsulfonyl; R, R¹, and R² are independentlyselected from hydrogen and lower alkyl; R³ is selected from hydrogen,lower alkyl, lower alkoxy and halogen and n is 0, 1 or 2; R⁴ is loweralkylene; R⁵ is benzothiazolyl which may be substituted with up to twogroups independently selected from Cl, Br, NO₂, lower alkyl, loweralkylamino, lower alkanoylamino, lower alkoxy, hydroxy, cyano, and -SCN.2. The compounds of claim 1 wherein R, R¹, R², and R³ are individuallyselected from hydrogen and methyl, X is cyano, R⁴ is ethylene, and R⁵ is2-benzothiazolyl.
 3. The compound according to claim 1 having theformula ##STR129##